Polyetherimide of improved color and process of preparing

ABSTRACT

A polyetherimide of improved color and processes for preparing the polyetherimide are disclosed.

This application is a national stage application of PCT/US2016/034597filed May 27, 2016, which claims priority to European Patent ApplicationNumber 15382288.7 filed May 29, 2015, both of which are herebyincorporated by reference in their entirety.

BACKGROUND

To meet the increased demand for polyetherimide, a new process wasinvented with a new chemistry route called the displacementpolymerization process. Synthesis of polyetherimide via the displacementpolymerization route generally includes imidization (e.g., U.S. Pat. No.6,235,866), diphenolic salt synthesis (e.g., U.S. Pat. No. 4,520,204)and polymerization (U.S. Pat. No. 6,265,521), followed by the downstreamactivities. In a specific embodiment of the displacement polymerizationprocess, the bisimide resulting from the reaction of 2 moles of achloro-substituted phthalic anhydride and 1 mole of metaphenylenediamine (the adduct abbreviated ClPAMI) polymerizes with bisphenol Adisodium salt (BPANa₂) in the presence of a phase transfer catalyst,such as hexaethylguanidinium chloride (HEGCl). HEGCl is a well-knownphase transfer catalyst to make polyetherimides. Utilization of HEGCl asa phase transfer catalyst at higher temperatures is described in U.S.Pat. No. 5,229,482.

It is desirable to improve the color quality (measured as YellownessIndex, or “YI”) of the polyetherimide made by the displacementpolymerization route. High color polymer requires more pigments and dyesto meet many color specifications, and the addition of excess colorantscan result in loss of other polymer physical properties. A low basepolymer color is therefore desirable.

There is an ongoing, unmet need for polyetherimides made by thedisplacement polymerization route having improved color properties, andmethods of making such chloro-substituted polyetherimides.

SUMMARY

A method for the manufacture of a polyetherimide composition isdisclosed, the method comprising contacting a bis(phthalimide) havingthe formula

with an alkali metal salt of a dihydroxy aromatic compound having theformula MO—Z—OM, in an oil-jacketed reactor, in the presence of acatalyst and 0 to 10% of a capping agent, and at an oil temperature of150° C. to 320° C., to form the polyetherimide comprising the structuralunits having the formula

wherein in the foregoing formulae X is fluoro, chloro, bromo, iodo,nitro or a combination thereof; R is an aromatic hydrocarbon grouphaving 6 to 27 carbon atoms, a halogenated derivative thereof, astraight or branched chain alkylene group having 2 to 10 carbon atoms, ahalogenated derivative thereof, a cycloalkylene group having 3 to 20carbon atoms, a halogenated derivative thereof, —(C₆H₁₀)_(z)— wherein zis an integer from 1 to 4, an aromatic hydrocarbyl moiety having from 1to 6 aromatic groups, and a divalent group of the formula

wherein Q¹ is —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— wherein y isan integer from 1 to 5, or a combination thereof; M is an alkali metal;Z is an aromatic C₆₋₂₄ monocyclic or polycyclic moiety optionallysubstituted with 1 to 6 C₁₋₈ alkyl groups, 1 to 8 halogen atoms, or acombination thereof; and n is an integer greater than 1; and wherein thepolyetherimide has a Yellowness Index of less than 93 to 50.

Also disclosed is a low color polyetherimide composition prepared viathe displacement reaction from a substituted phthalic anhydride and anorganic diamine at a temperature of 185° C. to 195° C. and mixing thereactor using an agitator with two sets of pitched turbine blades, witha blade to vessel diameter ratio range of about 0.45 to 0.65, at a speedin a range from about 40 to about 90 revolutions per minute, in areactor with a volume range from about 20 to 35 cubic meters, and acylindrical height to diameter ratio range of about 1.3 to about 1.6; orin another embodiment, wherein the agitator has two sets of 45° pitchedturbine blades with a blade to vessel diameter ratio of about 0.54 at aspeed in a range from about 70 to about 86 revolutions per minute in areactor with volume of about 28 cubic meters with a cylindrical heightto diameter ratio of about 1.45, wherein the polyetherimide has aYellowness Index of less than 93, or less than 80, or less than 70. Thepolyetherimide can have a Yellowness Index of as low as 50.

A low color polyetherimide composition is disclosed, prepared via adisplacement reaction from a substituted phthalic anhydride and anorganic diamine in which the polymerization is quenched with an acid ata temperature of from 145° C. to 155° C., wherein the polyetherimide hasa Yellowness Index of less than 93, or less than 80, or less than 70, oras low as 50.

A method for the manufacture of a polyetherimide composition isdisclosed, the method comprising: contacting a bis(phthalimide) havingthe formula

with an alkali metal salt of a dihydroxy aromatic compound having theformula MO—Z—OM, in an oil-jacketed reactor, in the presence of acatalyst and 0 to 10% of a capping agent, and at an oil temperature of150° C. to 320° C., and mixing the reactor using an agitator with twosets of pitched turbine blades, with a blade to vessel diameter ratiorange of about 0.45 to 0.65, at a speed in a range from about 40 toabout 90 revolutions per minute, in a reactor with a volume range fromabout 20 to 35 cubic meters, and a cylindrical height to diameter ratiorange of about 1.3 to about 1.6, quenching the polymerization with anacid at a temperature of from 130° C. to 200° C., to form apolyetherimide comprising structural units having the formula

wherein in the foregoing formulae, X is fluoro, chloro, bromo, iodo,nitro, or a combination thereof; R is an aromatic hydrocarbon grouphaving 6 to 27 carbon atoms, a halogenated derivative thereof, astraight or branched chain alkylene group having 2 to 10 carbon atoms, ahalogenated derivative thereof, a cycloalkylene group having 3 to 20carbon atoms, a halogenated derivative thereof, —(C₆H₁₀)_(z)— wherein zis an integer from 1 to 4, an aromatic hydrocarbyl moiety having from 1to 6 aromatic groups, and a divalent group of the formula

wherein Q¹ is —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— wherein y isan integer from 1 to 5, or a combination thereof; M is an alkali metal;Z is an aromatic C₆₋₂₄ monocyclic or polycyclic moiety optionallysubstituted with 1 to 6 C₁₋₈ alkyl groups, 1 to 8 halogen atoms, or acombination thereof; and n is an integer greater than 1; and wherein thepolyetherimide has a Yellowness Index of from less than 93 to 50.

These and other features, aspects, and advantages will become betterunderstood with reference to the following description and appendedclaims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the Mw versus time profiles for Examples 1-4.

FIG. 2 is a graph of polyetherimide color (YI units) versus conditions(Mild to Harsh).

FIG. 3 is a graph of polyetherimide molecular weight (Mz/Mw) versusconditions (Mild to Harsh).

FIG. 4 is a graph of polyetherimide color (YI units) versus temperature(° C.).

FIG. 5 is a cube plot for analysis of pellet YI for the full factorialdesign of 4 factors at 2 levels.

DETAILED DESCRIPTION

Downstream in the process of manufacturing a polyetherimide, the polymeris quenched with an acid such as phosphoric acid, in order to convert(via acidification) any remaining sodium phenoxide groups on the polymerchain into phenolic groups and sodium carboxylate groups into carboxylicacids. This ensures that there are no reactive groups remaining on thepolymer chain, which can impact negatively the efficiency of polymerfiltration and washing. The acid quench can be performed for a time of15 to 360 minutes, or, more specifically, 20 to 40 minutes, or, evenmore specifically, 25 to 35 minutes.

The invention provides an improved process which lowers the acidquenching temperature and improves color, measured by YI. There is animprovement of YI by decreasing the temperature from 170° C. to 150° C.,in another embodiment, the oil temperature is from about 145° C. toabout 155° C.

Controlling the reaction conditions during polymerization, specificallywall temperature and agitation, affects the final polymer yellownessindex (YI) and Mz/Mw. The mildest conditions (high speed agitation, andlower hot oil temperature) surprisingly gave a significantly lower YI aswell as a significantly lower ratio of z-average molecular weight toweight average molecular weight (Mz/Mw). In some embodiments, thereactor is heated using a jacket where hot oil circulates at atemperature in a range from about 150° C. to about 320° C. In anotherembodiment, the reactor is heated using a jacket where hot oilcirculates at a temperature in a range from about 180° C. to about 240°C., in another embodiment from 188° C. to 192° C.

Heat transfer in the commercial reactor from the heated jacket to thereaction mass is determined by a series of mechanisms: convectivetransfer by the hot oil flow in the jacket, conduction within the metalwall and convective transfer in the reactor volume. The largestresistance is given by the heat transfer from the wall to the bulk ofthe reactor volume. And this resistance is greatly impacted by theagitation in the reactor. The better the agitation, the higher the heattransfer per square meter for a given temperature gradient.Consequently, with poor mixing the hot oil temperature must be increasedin order to achieve the desired heat flux. Conversely, enhanced mixingenables a reduction of the hot oil temperature while maintaining thedesired heat flux.

In a non-homogeneous mixture, for example slurry contained in anagitated reactor, mixing needs to be sufficient to improve homogeneity,improve heat transfer, and avoid stagnation points on the vessel wallsand agitator shafts. If the reactor is operated with too low agitation,for example, the volume of stagnant zones can increase and poor masstransfer is expected. Conversely, too high agitation speed can create avortex around the agitator shaft, reduce the effective reaction volume,and produce excessive sidewall splash.

In a reactor, the interactions between substance properties (density,viscosity), agitator design, kinetics of reaction, and operatingvariables (agitator tip speed, wall temperature) can influence theextent of side reactions and therefore impact the final productproperties.

In some embodiments, the reactor is mixed using an agitator with twosets of pitched turbine blades, with a blade to vessel diameter ratiorange of about 0.45 to 0.65, at a speed in a range from about 40 toabout 90 revolutions per minute, in a reactor with a volume range fromabout 20 to 35 cubic meters, and a cylindrical height to diameter ratiorange of about 1.3 to about 1.6. In an another embodiment, the reactoris mixed using an agitator with two sets of 45° pitched turbine bladeswith a blade to vessel diameter ratio of about 0.54 at a speed in arange from about 70 to about 86 revolutions per minute in a reactor withvolume of about 28 cubic meters with a cylindrical height to diameterratio of about 1.45.

The polyetherimides are of formula (1)

wherein n is greater than 1, for example, 10 to 1,000 or more, or morespecifically 10 to 50; or for example 2 to 1000, or 5 to 500, or 10 to100.

The group R in formula (1) is independently the same or different, andis a substituted or unsubstituted divalent organic group, for example,an aromatic hydrocarbon group having 6 to 27 carbon atoms, a halogenatedderivative thereof, a straight or branched chain alkylene group having 2to 10 carbon atoms, a halogenated derivative thereof, a cycloalkylenegroup having 3 to 20 carbon atoms, a halogenated derivative thereof,—(C₆H₁₀)_(z)— wherein z is an integer from 1 to 4, an aromatichydrocarbyl moiety having from 1 to 6 aromatic groups, or a divalentgroup of the formula (2)

wherein Q¹ is —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— wherein y isan integer from 1 to 5, or a combination thereof. In some embodiments Ris divalent group of one or more of the following formulas (2a)

wherein Q¹ is —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— wherein y isan integer from 1 to 5 or a halogenated derivative thereof (whichincludes perfluoroalkylene groups), or —(C₆H₁₀)_(z)— wherein z is aninteger from 1 to 4. In some embodiments R is m-phenylene, p-phenylene,or a diarylene sulfone, in particular bis(4,4′-phenylene)sulfone,bis(3,4′-phenylene)sulfone, bis(3,3′-phenylene)sulfone, or a combinationcomprising at least one of the foregoing. In some embodiments, at least10 mole percent of the R groups contain sulfone groups, and in otherembodiments no R groups contain sulfone groups.

Further in formula (1), the divalent bonds of the —O—Z—O— group are inthe 3,3′,3,4′,4,3′, or the 4,4′ positions, and Z is an aromatic C₆₋₂₄monocyclic or polycyclic moiety optionally substituted with 1 to 6 C₁₋₈alkyl groups, 1 to 8 halogen atoms, or a combination comprising at leastone of the foregoing, provided that the valence of Z is not exceeded.Exemplary groups Z include groups of formula (3)

wherein R^(a) and R^(b) are each independently the same or different,and are a halogen atom or a monovalent C₁₋₆ alkyl group, for example; pand q are each independently integers of 0 to 4; c is 0 to 4; and X^(a)is a bridging group connecting the hydroxy-substituted aromatic groups,where the bridging group and the hydroxy substituent of each C₆ arylenegroup are disposed ortho, meta, or para (specifically para) to eachother on the C₆ arylene group. The bridging group X^(a) can be a singlebond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—, or a C₁₋₁₈ organic bridginggroup. The C₁₋₁₈ organic bridging group can be cyclic or acyclic,aromatic or non-aromatic, and can further comprise heteroatoms such ashalogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The C₁₋₁₈organic group can be disposed such that the C₆ arylene groups connectedthereto are each connected to a common alkylidene carbon or to differentcarbons of the C₁₋₁₈ organic bridging group. A specific example of agroup Z is a divalent group of formula (3a)

wherein Q is —O—, —S—, —SO₂—, —SO—, or —C_(y)H_(2y)— wherein y is aninteger from 1 to 5 or a halogenated derivative thereof (including aperfluoroalkylene group). In a specific embodiment Z is a derived frombisphenol A, such that Q in formula (3a) is 2,2-isopropylidene.

In another embodiment, the polyetherimide comprises more than 1,specifically 10 to 1,000, or more specifically, 10 to 50 structuralunits, of formula (1) wherein R is a divalent group of formulas (3)wherein Q¹ is —C_(y)H_(2y)— wherein y is an integer from 1 to 5 or ahalogenated derivative thereof, and Z is a group of formula (4a). Insome embodiments, R is m-phenylene, p-phenylene, p-arylenediphenylsulfone, or a combination thereof, and Z¹ is2,2-(4-phenylene)isopropylidene. An example of a polyetherimide sulfonecomprises structural units of formula (1) wherein at least 50 molepercent of the R groups are of formula (2) wherein Q is —SO₂— and theremaining R groups are independently p-phenylene or m-phenylene or acombination comprising at least one of the foregoing; and Z¹ is2,2-(4-phenylene)isopropylidene.

In some embodiments, the polyetherimide is a copolymer that optionallycomprises additional structural imide units that are not polyetherimideunits, for example imide units of formula (4)

wherein R is as described in formula (1) and each V is the same ordifferent, and is a substituted or unsubstituted C₆₋₂₀ aromatichydrocarbon group, for example a tetravalent linker of the formulas

wherein W is a single bond, —S—, —SO₂—, —SO—, or —C_(y)H_(2y)— wherein yis an integer from 1 to 5 or a halogenated derivative thereof (whichincludes perfluoroalkylene groups). These additional structural imideunits preferably comprise less than 20 mol % of the total number ofunits, and more preferably can be present in amounts of 0 to 10 mol % ofthe total number of units, or 0 to 5 mol % of the total number of units,or 0 to 2 mole % of the total number of units. In some embodiments, noadditional imide units are present in the polyetherimide.

The polyetherimides are prepared by the so-called “displacement” method.In this method, a substituted phthalic anhydride of formula (7)

wherein X is a halogen or a nitro group, is condensed (imidized) with anorganic diamine of the formula (8)H₂N—R—NH₂  (8)wherein R is as described in formula (1), to form a bis(phthalimide) offormula (9).

In some embodiments, X is a halogen, specifically fluoro, chloro, bromo,or iodo, or X is nitro. Preferably X is a halogen to provide abis(halophthalimide), more preferably chloro to providebis(chlorophthalimide). A combination of different X groups, preferablyhalogens, can be used.

Illustrative examples of amine compounds of formula (8) include1,4-butane diamine, 1,5-pentanediamine, 1,6-hexanediamine,1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine,1,10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine,3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine,4-methylnonamethylenediamine, 5-methylnonamethylenediamine,2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine,3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy) ethane,bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamine,bis-(4-aminocyclohexyl) methane, m-phenylenediamine, p-phenylenediamine,2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine,p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine,5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine,3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 1,5-diaminonaphthalene,bis(4-aminophenyl) methane, bis(2-chloro-4-amino-3, 5-diethylphenyl)methane, bis(4-aminophenyl) propane, 2,4-bis(b-amino-t-butyl) toluene,bis(p-b-amino-t-butylphenyl) ether, bis(p-b-methyl-o-aminophenyl)benzene, bis(p-b-methyl-o-aminopentyl) benzene, 1,3-diamino-4-isopropylbenzene, bis(4-aminophenyl) ether and1,3-bis(3-aminopropyl) tetramethyldisiloxane. Mixtures of these aminescan be used. Illustrative examples of amine compounds of formula (8)containing sulfone groups include 4,4′-diamino diphenyl sulfone (DDS)and bis(aminophenoxy phenyl) sulfones (BAPS). Any regioisomer of theforegoing compounds can be used. C₁₋₄ alkylated or poly(C₁₋₄)alkylatedderivatives of any of the foregoing can be used, for example apolymethylated 1,6-hexanediamine Combinations comprising any of theforegoing amines can be used.

Specifically, diamine (8) is a meta-phenylene diamine (8a) or apara-phenylene diamine (8b)

wherein R^(a) and R^(b) are each independently a halogen atom, nitro,cyano, C₂-C₂₀ aliphatic group, C₂-C₄₀ aromatic group, and a and b areeach independently 0 to 4. Examples include meta-phenylenediamine (mDA),para-phenylenediamine (pDA), 2,4-diaminotoluene, 2,6-diaminotoluene,2-methyl-4,6-diethyl-1,3-phenylenediamine,5-methyl-4,6-diethyl-1,3-phenylenediamine,1,3-diamino-4-isopropylbenzene, and 4,4′-diamino diphenyl sulfone. Insome embodiments, diamine (8) is meta-phenylene diamine, para-phenylenediamine, 4,4′-diamino diphenyl sulfone, and a combination thereof.

Condensation of substituted phthalic anhydride (7) and diamine (8)(imidization) can be conducted in the absence or presence of a catalyst.

The reaction is generally conducted in the presence of a relativelynon-polar solvent, preferably with a boiling point above 100° C.,specifically above 150° C., for example, o-dichlorobenzene,dichlorotoluene, 1,2,4-trichlorobenzene, diphenyl sulfone, amonoalkoxybenzene such as anisole, veratrole, diphenylether, orphenetole. Ortho-dichlorobenzene and anisole can be particularlymentioned.

The bis(phthalimide)s (9) are generally prepared at least 110° C.,specifically 150° C. to 275° C., more specifically 175° C. to 225° C. Attemperatures below 110° C., reaction rates may be too slow foreconomical operation. Atmospheric or super-atmospheric pressures can beused, for example, up to 5 atmospheres, to facilitate the use of hightemperatures without causing solvent to be lost by evaporation.

The solvent, diamine (8), and substituted phthalic anhydride (7) can becombined in amounts such that the total solids content during thereaction to form bis(phthalimide) (9) does not exceed 25 wt. %, or 17wt. %. “Total solids content” expresses the proportion of the reactantsas a percentage of the total weight, including liquids, present in thereaction at any given time.

In general practice, a molar ratio of substituted phthalic anhydride (7)to diamine (8) of 1.98:1 to 2.2:1, specifically 1.98:1 to 2.1, or about2:1 is used. According to the invention a slight excess of anhydride isdesired to improve the color of the final product. A properstoichiometric balance between substituted phthalic anhydride (7) anddiamine (8) is maintained to prevent undesirable by-products that canlimit the molecular weight of the polymer, and/or result in polymerswith amine end groups. Accordingly, in some embodiments, imidizationproceeds adding diamine (8) to a mixture of substituted phthalicanhydride (7) and solvent to form a reaction mixture having a targetedinitial molar ratio of substituted phthalic anhydride to diamine;heating the reaction mixture to a temperature of at least 100° C.(optionally in the presence of an imidization catalyst); analyzing themolar ratio of the heated reaction mixture to determine the actualinitial molar ratio of substituted phthalic anhydride (7) to diamine(8); and, if necessary, adding substituted phthalic anhydride (7) ordiamine (8) to the analyzed reaction mixture to adjust the molar ratioof substituted phthalic substituted phthalic anhydride (7) to diamine(8) to 1.98:1 to 2.2:1, preferably 2.0 to 2.1.

After imidization, the bis(phthalimide) (9) is polymerized by reactionwith an alkali metal salt of a dihydroxy aromatic compound to providethe polyetherimide (1). In particular, the leaving group X ofbis(phthalimide) (9)

is displaced by reaction with an alkali metal salt of a dihydroxyaromatic compound of formula (10)M¹O—Z—OM¹  (10)wherein M¹ is an alkali metal and Z is as described in formula (1), toprovide the polyetherimide of formula (1)

wherein n, R, and Z are as defined above.

Alkali metal M¹ can each independently be any alkali metal, for example,lithium, sodium, potassium, and cesium, and can be the same as M²(infra). Thus alkali metal salt (10) is lithium salts, sodium salts,potassium salts, cesium salts, and a combination thereof. In someembodiments the metals are potassium or sodium. In some embodiments, M¹is sodium. The alkali metal salt (10) can be obtained by reaction of themetal hydroxide or carbonate with an aromatic dihydroxy compound offormula (4), specifically an aromatic C₆₋₂₄ monocyclic or polycyclicdihydroxy compound optionally substituted with 1 to 6 C₁₋₈ alkyl groups,1 to 8 halogen atoms, or a combination thereof, for example, a bisphenolcompound of formula (11)

wherein R^(a), R^(b), and X^(a) are as described in formula (3). In someembodiments, the dihydroxy compound corresponding to formulas (4a) canbe used. The compound 2,2-bis(4-hydroxyphenyl) propane (“bisphenol A” or“BPA”) can be used.

The polymerization can be conducted in the presence of a capping agent,in particular an alkali metal salt of a monohydroxy aromatic compound offormula (12)M²-O—Z²  (12)wherein M² is an alkali metal and Z² is derived from a monohydroxyaromatic compound (13) described below. It has been found by theinventors hereof that when the amount of the monohydroxy aromatic salt(12) is greater or equal to 5 mole percent, based on the total moles ofthe alkali metal salts (10) and (12), a polyetherimide having a weightaverage molecular weight from more than 200 to less than 43,000 Daltonscan be obtained as further described below.

Further, as described in more detail below, the polyetherimides can havelow residual content and good physical properties when a capping agentis used. The amount of monohydroxy aromatic salt (12) can be from 0 to15 mole percent, including up to 15 mole %, or from 3 to 15 molepercent, or from 6 to 15 mole percent, or from 6 to 10 mole percent,based on the total moles of the alkali metal salts (10) and (12). Forexample, the amount of monohydroxy aromatic salt (12) can be greaterthan or equal to 5 mole percent to 15, 14, 13, 12, 11, 10, 9, 8, or 7mole percent.

Alkali metal M² can be any alkali metal, for example, lithium, sodium,potassium, and cerium, and is generally the same as the alkali metal M¹.Thus alkali metal salt (12) is lithium salts, sodium salts, potassiumsalts, cesium salts, and a combination thereof. In some embodiments, themetals are potassium or sodium. In some embodiments, M² is sodium. Thealkali metal salt (12) can be obtained by reaction of the metal M² witharomatic C₆₋₂₄ monocyclic or polycyclic monohydroxy compound optionallysubstituted with 1 to 6 C₁₋₈ alkyl groups, 1 to 8 halogen atoms, or acombination thereof, for example, a monohydroxy aromatic compoundformula (13)

wherein R^(c) and R^(d) are each independently a halogen atom or amonovalent hydrocarbon group, for example a monovalent C₁₋₆ alkyl group;r and s are each independently integers of 0 to 4; c is zero to 4; t is0 or 1; when t is zero, X^(b) is hydrogen or a C₁₋₁₈ alkyl group; andwhen t is 1, X^(b) is a single bond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—,or a C₁₋₁₈ organic bridging group. The C₁₋₁₈ organic bridging group canbe cyclic or acyclic, aromatic or non-aromatic, and can further compriseheteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, orphosphorous. The C₁₋₁₈ organic bridging group can be disposed such thatthe C₆ arylene groups connected thereto are each connected to a commonalkylidene carbon or to different carbons of the C₁₋₁₈ organic bridginggroup. In some embodiments, t is zero and X^(b) is hydrogen or a C₄₋₁₂alkyl group or t is one and X^(b) is a single bond or a C₁₋₉ alkylenegroup.

For example Z² is a group of formulas

or a combination comprising at least one of the foregoing.

In some embodiments, Z and Z² are each independently a C₁₂₋₂₄ polycyclichydrocarbyl moiety optionally substituted with 1 to 6 C₁₋₆ alkyl groups.In some embodiments, M¹ and M² are each sodium. For example, Z is adivalent group having formula

andZ² is a monovalent group having formula

wherein Q^(a) and Q^(b) are each independently a single bond, —O—, —S—,—C(O), —SO₂, —SO—, —C_(y)H_(2y)— wherein y is an integer from 1 to 5,—(C₆H₁₀)_(z)— wherein z is an integer from 1 to 4; and a halogenatedderivative thereof. In other embodiments, Q^(a) and Q^(b) are the same,e.g., isopropylidene.

Polymerization by reaction of bis(phthalimide) (9) with a combination ofalkali metal salts (10) and (12) can be in the presence of phasetransfer catalyst that is substantially stable under the reactionconditions used, in particular temperature. Exemplary phase transfercatalysts for polymerization include hexaalkylguanidinium andα,ω-bis(pentaalkylguanidinium)alkane salts. Both types of salts can bereferred to herein as “guanidinium salts.”

Polymerization is generally conducted in the presence of a relativelynon-polar solvent, preferably with a boiling point above 100° C.,specifically above 150° C., for example, o-dichlorobenzene,dichlorotoluene, 1,2,4-trichlorobenzene, diphenyl sulfone, amonoalkoxybenzene such as anisole, veratrole, diphenylether, orphenetole. Ortho-dichlorobenzene and anisole can be particularlymentioned.

Polymerization can be conducted at least 110° C., specifically 150° C.to 275° C., more specifically 175° C. to 225° C. At temperatures below110° C., reaction rates may be too slow for economical operation.Atmospheric or super-atmospheric pressures can be used, for example, upto 5 atmospheres, to facilitate the use of high temperatures withoutcausing solvent to be lost by evaporation.

In some embodiments, the combination of alkali metal salts (10) and (12)is added directly to the composition containing the bis(phthalimide) (9)in organic solvent. Water removal from the system can be accomplished ineither batch, semi-continuous or continuous processes using means knownin the art such as a distillation column in conjunction with one or morereactors. In some embodiments, a mixture of water and non-polar organicliquid distilling from a reactor is sent to a distillation column wherewater is taken off overhead and solvent is recycled back into thereactor at a rate to maintain or increase the desired solidsconcentration. Other methods for water removal include passing thecondensed distillate through a drying bed for chemical or physicaladsorption of water.

The molar ratio of the bis(phthalimide) (9) to the alkali metal salt(10) can be 0.9:1 to 1.1:1.0. A solids content of the bis(phthalimide)(9) in the polymerization can be 15 wt. % to 25 wt. %, based on thetotal weight of the polymerization mixture.

EXAMPLES

The materials in Table 1 were used or made in the following Examples andComparative Examples.

TABLE 1 Acronym Description Source PA Phthalic anhydride 3-ClPA3-Chlorophthalic anhydride SABIC 4-ClPA 4-Chlorophthalic anhydride SABICClPA Mixture of 3-chlorophthalic SABIC anhydride and 4-chlorophthalicanhydride ClPAMI 1,3-bis[N-(4-chlorophthalimido)]- Examples benzeneMono-ClPAMI Mixture of Examples (MA) 1-amino-3-N-(4-chlorophthalimido)-benzene, 1-amino-3-N- (3-chlorophthalimido)benzene mPD meta-Phenylenediamine DuPont DDA 4,4′-diaminodiphenyl sulfone Atul BPA2,2-Bis(4-hydroxyphenyl)propane, Chiba/CTG (Bisphenol A) BPANa₂Bisphenol A, disodium salt SABIC PEI Polyetherimide Examples o-DCBortho-Dichlorobenzene Fischer HEGCl or KEG Hexaethylguanidinium chlorideSABIC SPP Sodium phenylphosphinate Akzo PEG Pentaethylguanidine ExamplesNaOH Sodium hydroxide Sigma Aldrich KP Tri-potassium phosphate SigmaAldrichProperty Testing

Weight average molecular weight (Mw) of the polymer product wasdetermined by gel permeation chromatography (GPC) using polystyrenestandards. Mz is the z-average molecular weight.

APHA is a single number Yellowness Index used for measuring yellowcoloration in nearly white liquid samples. APHA index values weredetermined in accordance with ASTM D1209. Samples of solutions asreported below were analyzed with a Gretag Macbeth Color Eye 7000Ainstrument. The instrument readings thus obtained are reported assolution APHA values. In some cases, the solution APHA value wasinserted into a formula to yield a calculated estimate of a dry APHAvalue.

To measure APHA of BPANa₂ salt, 2 grams of BPANa₂ aqueous solution oroDCB slurry was taken and diluted up to 100 mL using acetonitrile-watermixture (60:40, v/v). After analyzing the sample for APHA using a GretagMacbeth Color Eye 7000A instrument, the instrument reading was convertedAPHA based on the dry weight of BPANa₂ salt as follows:APHA=(Solution APHA×100)/(Sample weight×solid wt. %)  Eq. (1)All APHA values reported for BPANa₂ salt were calculated based onequation (1).

Generally, the solution YI is a number calculated fromspectrophotometric data that describes the color of a test sample asbeing clear or white (low solution YI) versus being more yellow (highsolution YI). Sample handling and preparation can affect the testresults. The yellowness index of polyetherimide polymer was determinedby measuring the solution YI of the resulting solution on a GretagMacbeth Color Eye 7000A instrument. The instrument reading was referredto as solution YI. The YI values reported and claimed are predictedplaque YI calculated based on the following correlation:Predicted Plaque YI=(Solution YI+18.2)/0.5986  Eq. (2)

Where indicated, “dry o-DCB” having moisture content of less than 10 ppmwas used in the reactions. The dry o-DCB was kept in a glove box over4-Angstrom molecular sieves.

Gretag Macbeth Color Eye 7000A instrument was used to measure thesolution APHA color as well as Yellowness Index (YI) of polymersolution.

General Procedures

BPANa₂ Salt Synthesis at Lab Scale

A. BPANa₂ Salt Synthesis in Water

Before starting BPANa₂ salt synthesis, N₂ was bubbled overnight throughde-mineralized water (about 1 liter in a round bottom flask) to removedissolved oxygen. Once the de-oxygenated water was ready, a 4-neck1-liter round bottom flask was transferred to a glove box (under N₂environment) along with all the raw materials. Then 41.9 grams of BPA,14.7 grams of NaOH and 449 grams of de-oxygenated water were chargedinto the RB flask at room temperature, along with a magnetic stirrer,and a condenser was fixed on the top of the flask. The flask was takento a hood, immersed in an oil bath, and mild magnetic stirring wasapplied. When the reaction mixture was under mild magnetic stirring, thewhole system was then kept under a nitrogen environment for about 30minutes at room temperature to remove oxygen. Then the oil bathtemperature was raised to 70° C. to 80° C. and N₂ sweep was provided tomaintain inert atmosphere during the course of the reaction. Theapproximate solid weight % of the BPANa₂ salt was around 21%. The systemwas kept under total reflux conditions to prevent water losses duringreaction. Typically after 1 hour the reaction mass became clear,indicating completion of BPANa2 salt formation.

To track the BPANa₂ salt quality over time, samples of BPANa₂ saltsolution were checked at regular time intervals for APHA value and thestoichiometry of the reaction. Based on stoichiometry, corrections weremade (either BPA or NaOH) to maintain the desired stoichiometry forBPANa₂ salt. The obtained solution APHA was converted on the dry basisbased on equation (1). The calculated APHA value is also referred to asAPHA of BPANa₂ (aqueous stage).

B.: Solvent Swapping into oDCB

Before starting the solvent swapping, oDCB (0.5 to 1 liter) was agitatedwhile applying 150° C. heating oil temperature under N₂ sweep for about0.5 to 1 hour to remove any dissolved oxygen. Aqueous BPANa₂ saltsolution from step A was added drop wise to oDCB. The aqueous BPANa₂salt solution feed temperature was maintained at about 70° C. to avoidthe precipitation of BPANa₂ salt, which may create operationaldifficulties while performing solvent swapping. Water along with theoDCB was collected overhead in the Dean-Stark. Dry ODCB was added to thereactor while water/oDCB was boiled off to maintain the desired percentsolids of BPANa₂ in oDCB. The total time required for swapping 21 wt. %aqueous BPANa₂ salt (100 g batch size) solution was around 5 to 6 hours.After completion of the swapping, the BPANa₂ salt solution temperaturewas increased slowly to 190° C. for the removal of water-oDCB mixture,and maintained until the collected water-oDCB mixture reached a moisturecontent of 200 to 400 ppm.

C. Homogenization

The oDCB BPANa₂ salt slurry was allowed to cool down to room temperatureand then transferred to a 1 liter glass bottle under N₂ environment. Alab scale IKA homogenizer (Model: T25 Ultra Turrax) was operatedintermittently to homogenize the oDCB based BPANa₂ salt solution at aspeed of 8,000 to 9,000 rpm for about 1 hour (instead of usinghomogenizer continuously, to avoid local heating, it needed to beswitched off after every 15 minutes of use for about 5 to −10 minutes).This homogenization operation was carried out under N₂ environment atroom temperature.

D. Drying

The homogenized BPANa₂ salt was then transferred into either a 1 or2-liter 5-neck round bottom (RB) flask. For those runs in whichtripotassium phosphate (KP) had not been added to BPANa₂ salt during thesolvent swapping stage, KP in the form of a dry oDCB based slurry withparticle size distribution (PSD) of less than 70 micron was then added(1.25 wt. % based on the final polymer weight) at room temperature tothe homogenized BPANa₂. The 1.25 wt. % excess KP amount was decidedbased on the observed —OH end group concentration in the final polymer,which should be less than 100 ppm. Particle size of KP was critical toachieve the OH end group specification in the final polymer. N₂ was thenbubbled through the solution for about 1 to 2 hours at room temperatureto remove any oxygen which may have been introduced with the KP slurryor the homogenized BPANa₂ salt slurry.

Then the final BPANa₂ salt drying was started by adjusting the oil bathtemperature to 190° C. to 195° C. The reaction temperature wasmaintained until the oDCB collected overhead from the system met thewater content specification (less than 20 ppm). Then heating was stoppedand the BPANa₂ salt solution was cooled down to room temperature. Laterit was stored under N₂ environment inside a glove box at roomtemperature. Finally the solid percentage of the BPANa₂ salt wasmeasured using HCl titration method. Based on this solid wt. % andmeasured solution APHA of BPANa₂, APHA on dry BPANa₂ salt basis wascalculated. The calculated APHA is also referred to as APHA of BPANa₂(after drying).

BPANa₂ Salt Synthesis at Pilot Scale

A. Aqueous BPANa₂ Salt Reaction

BPA addition: The required quantity of water to maintain about 25 wt. %of BPANa₂ salt was added into an aqueous salt reactor. It was thenheated to about 70° C. to 80° C. under N₂ bubbling for 2 hours to removeoxygen dissolved in the water. A stoichiometric quantity of BPA wasadded into the pool of hot water at about 80° C. via hopper in theaqueous reactor.

Caustic lye preparation: The required amount of deoxygenated water tomake about 40 wt. % NaOH solution was drained from the aqueous BPANa₂salt reactor prior to BPA addition into a small vessel. The pre-weighedNaOH pellets were added slowly to the small vessel to make caustic lyesolution. Preparation of caustic lye solution is an exothermic reaction,so adequate care was taken to minimize the water loss duringpreparation. The small vessel was cooled with an external ice bath. Thecaustic lye solution thus prepared was charged into the caustic lye tankwhich was maintained at room temperature. A continuous N₂ bubbling waspresent through the caustic lye tank until the addition of caustic lyeinto the aqueous reactor started.

Aqueous reaction: After completion of the BPA addition into the aqueousBPANa₂ salt reactor, it was purged with N₂ for at least 1 hour to removeany residual oxygen from the reaction mixture. After 1 hour of N₂bubbling, the reactor temperature was decreased to about 70° C. to 74°C. Subsequently the caustic lye tank was pressurized (about 1 to 1.5barg) and it was charged to BPANa₂ reactor over a period of 20 to 30minutes via a sparger line. As the caustic lye was added, the reactortemperature was allowed to increase by 3° C. to 5° C. due to reactionexotherm. During the initial set of experiments NaOH flakes were chargedthrough a hopper as solid instead of solution. Sufficient care was takento maintain temperature of the reactor contents below 82° C. bymonitoring the rate of NaOH addition. Changing to the addition of lyevia sparger helped to minimize the color formation in aqueous BPANa₂salt and also reduced the water loss due to evaporation.

After the completion of NaOH addition, the temperature of the reactionwas increased to 80° C. to 85° C. After 1 hour from the completion ofcaustic lye addition, a sample was removed from the reactor to measurethe stoichiometry of the reactant residuals (stoic. specification 97 to105 mg/L BPA in toluene). If the reaction was not on stoichiometryspecification (“on stoic.”), corresponding quantities of reactant (BPAor NaOH), as indicated by the BPA salt stoichiometry calculator, wasadded into the reactor. One hour after the stoic correction, a samplewas drawn again and checked for the stoic. The sample was analyzed forAPHA to measure the BPANa₂ salt color at the aqueous stage. Thisprocedure of sampling, analysis, and stoic correction was repeated untilthe reaction was on stoic. The on stoic reactor mixture marked thecompletion of the reaction. The resulting mixture was ready for solventswapping.

B. Primary Drier (Solvent Swapping) and Homogenization

Once the aqueous BPANa₂ salt reaction was considered complete, theaqueous BPANa₂ salt reactor was pressurized to about 4 barg and theBPANa₂ salt solution was sprayed via spray nozzles into a primary drier(1st drier) containing a pool of hot oDCB at 130° C. to 145° C. The 1stdrier was always maintained under N₂ purge (about 8 to 10 Kg/hr of N₂).As the BPANa₂ salt solution was sprayed, free water (unbound water) wasquickly evaporated and the BPANa₂ precipitated as a white solid in oDCB.During the course of solvent swapping, the quantity of oDCB lost withwater due to azeotropic boiling was replaced with fresh oDCB from thedry oDCB storage vessel (earlier oDCB was stored either at 175° C. or145° C.) so as to maintain a constant percentage solid (13%) of theresulting BPANa₂ salt slurry.

After the completion of BPANa₂ salt spray, the temperature of the 1stdrier was increased to remove the free moisture by stripping of oDCB atits boiling temperature (176° C.). Once the moisture measured in thevapor condensate was decreased to less than 200 ppm, the 1st driertemperature was decreased to 140° C. to 150° C. The BPANa₂ salt slurryin oDCB was re-circulated using a pump via a homogenizer (grinder) toreduce the particle size of BPANa₂ salt. After 1 hour of homogenization,a pre-homogenized KP slurry in oDCB was pumped into the drier. Duringthe course of homogenization, BPANa₂ salt samples were withdrawn andchecked for the particle size distribution. The homogenization wascontinued until the BPANa₂ salt particles met the process specification(particle size spec. less than 75 microns), normally at the end of 2.5hours. The same sample was analyzed for APHA to track the color of theBPANa₂ salt.

C. Secondary Drier

The relatively dry slurry (less than 200 ppm moisture) from the 1ststage drier, at about 15% solids, was transferred to a 2nd stage dryerto remove the residual moisture before its use in polymerization. Afterthe transferring of the BPANa₂ salt was complete, the temperature of the2nd stage dryer was increased to 176° C. to remove any bound or unboundmoisture from the BPANa₂ salt slurry. Again at this stage the oDCB lostdue to azeotropic boiling with water was compensated by charging hot dryoDCB from the header into the 2nd drier. During the course of drying,samples were drawn and analyzed for moisture by Karl Fisher titration.Once the BPANa₂ salt slurry was dried to less than 20 ppm moisture, theBPANa₂ salt slurry was concentrated to a desired level, for example,about 15% by driving off oDCB. After the BPANa2 salt concentration wascompleted, the temperature of BPANa₂ salt slurry was decreased to about150° C. and stored under nitrogen atmosphere until used in thepolymerization step. The concentrated BPANa2 salt slurry sample waswithdrawn to measure the BPANa₂ salt solid wt. % in oDCB and APHA color.In a further simplification of the process, both drying stages can beconducted in a single drier.

Imidization

A typical ratio of raw materials charged during the course ofimidization and then polymerization are provided in Table 2.

TABLE 2 Raw material Value UOM mPD/ClPA 29.6  % wt. PA/ClPA 0.9 % wt.HEGCl/Polymer 0.8 to 1 % mol BPA Salt/mPD 2.5 kg/kgLab Scale Protocol

Wet oDCB was charged into a reactor, equipped with a mechanical stirrer,a solids addition port, an overhead line with condenser, variousaddition nozzles, and means to maintain a nitrogen atmosphere. Thequantity of oDCB used in a particular reaction was based on the desiredpercentage solids of the imidization reaction.

After charging oDCB, all the raw materials (mPD, PA and ClPA (95:5mixture of 4-ClPA and 3-ClPA) were charged into the reactor at roomtemperature (25° C.). The mixture was kept under continuous nitrogensweep for an hour to de-oxygenate the system. The temperature of thereaction was then slowly raised to 176° C. in steps within an hour.

Pilot Scale Protocol

After charging oDCB, the temperature of the reactor was increased toabout 120° C. During this time oDCB was degassed by bubbling nitrogenthrough it. When the temperature reached 120° C., ClPA and PA werecharged manually through the reactor's hopper. Subsequently the hopperwas flushed by oDCB. Next, the temperature of the reactor was increasedto about 160° C. over a period of 45 minutes. The reactor was held atthis temperature for about 30 minutes to ensure a homogeneous mixture inthe reactor. During this time nitrogen was bubbled through the reactantmixture to remove any dissolved gases.

Another vessel was charged with mPD and oDCB at room temperature. Themixture was bubbled with nitrogen for 2 hours, and then heated to 75° C.to 80° C. to provide a solution of mPD dissolved in oDCB (solid wt. %=25to 27%). The mPD solution thus prepared was charged slowly into theimidization reactor at about 160° C. over a period of 45 minutes. Aftercompletion of the mPD addition, the temperature of the reactor wasincreased to about 170° C. to 175° C. and was held at this condition forthe duration of the reaction. During this period, mPD reacted with ClPAto provide oDCB based ClPAMI slurry containing intermediate products ofthis reaction and water as byproduct. Water vapors leaving the reactoralong with oDCB were condensed and collected in the collection pot. Atthe end of 2 hours, an aliquot sample was drawn to measure thestoichiometry of the reaction. The following species are analyzed forstoichiometry calculations: 4-chlorophthalic acid, 3-chlorophthalicacid, phthalic acid, 4-chlorophthalic anhydride, 3-chlorophthalicanhydride, phthalic anhydride, 4-monoamine, 3-monoamine, and phthalicanhydride monoamine.

The stoichiometry of ClPAMI was calculated using the analysis data forthe above chemical species and the appropriate reactant (either ClPA ormPD, referred as stoic correction) were charged to achieve the desiredstoichiometry in the imidization reactor. After 1 hour from thecompletion of stoic correction, a sample was drawn again for measuringthe stoic. This activity of sampling and stoic correction was repeateduntil the desired reaction spec was achieved. Once the reaction was onspec, the ClPAMI was dried to less than 20 ppm moisture in thecondensate by stripping of oDCB. The on stoic, dried ClPAMI thusprepared marked the completion of imidization reaction. Generally, theClPAMI/oDCB slurry was about 13 to 17% solids. Once the moisturespecification was achieved, ClPAMI was considered ready forpolymerization. The oDCB was continuously distilled out of the system todry ClPAMI.

The ClPAMI made above was purified by isolating it from the solvent andother soluble impurities, and washed with different solvents or solventmixture. The solid ClPAMI powder was then dried (at 150° C. under vacuumfor 5 to 6 hours) and charged to the polymerization reactor.

Polymerization

Process 1

Once the ClPAMI was on stoic then it was dried to achieve less than 20ppm moisture. Then 1 mole % HEGCl (containing about 500 to 1,000 ppmmoisture) was added to ClPAMI and the mixture was dried to less than 20ppm moisture. Once the dried ClPAMI met all the specs (Stoic: −0.1 to0.3 mole % ClPA rich, r-MA less than 0.04 mole %), dry BPANa₂ salt wasadded (maintained at 165° C. to 170° C.) over a period of about 30 to 60min to start the polymerization.

Polymer Isolation and Purification

After the completion of the polymerization reaction, the polymer masswas diluted to approximately 10 wt. % with dry oDCB. A desired amount ofH₃PO₄ (85 wt. % in water) was then added to quench the polymer reactionmass at 165° C. to 170° C. This changed the reaction mass colordrastically. Once the reaction mass pH was less than 3, it was assumedthat the quenching was done. The total quenching time was about an hour.After quenching, the reaction mass was cooled down to room temperatureand passed through vacuum filter assembly to remove the NaCl out of thesystem. The clear filtrate was then analyzed for solid % and solutionYellowness Index (YI).

Examples 1-4

These examples show that controlling the reaction conditions duringpolymerization, specifically the wall temperature of the reactor and theagitation rate, affects the final polymer YI and Mz/Mw. The mildestconditions (high speed agitation, and lower hot oil temperature)surprisingly gave a significantly lower YI and a significantly lowerMz/Mw as well. A lower Mz/Mw indicates a polymer that is less branched.When molded, a branched polymer behaves different rheologically than aless branched or unbranched polymer. These differences can negativelyaffect molding cycle times. Branched polymers may become non-processableif processing conditions were to increase branching even slightly. Forexample, when a branched polymer is molded at a slightly higher thannormal temperature, more branching of the polymer can occur duringmolding, resulting in a cross-linked part with decreased tensilestrength and impact resistance.

Controlled polymerization reactions were performed in a 3 LiterHastelloy autoclave reactor. All reactions were filtered and washed 2times. The hot oil temperature, agitation speed and the quality of theBPANa₂ were varied as shown in Table 3 for Examples 1-4. The followingvariables were kept constant during the experiments: ClPAMI source,polymerization procedure (polymerization process 1), final MW of PEI(40-45 kDa), and total reaction time.

TABLE 3 Example No. X1: Reaction Conditions¹ X2: BPA Salt quality² 1 + +2 − + 3 − − 4 + − ¹X1 (−): 1,000 rpm + 190° C. hot oil temperature ¹X1(+): 300 rpm + 220° C. hot oil temperature ²X2 (−): BPA Salt 100% APHAcolor 63 ²X2 (+): BPA Salt 100% APHA color 219

The Mw versus time profiles for Examples 1-4 are shown in FIG. 1. Theobjective was to reach similar final Mw (40 kDa to 45 kDa) together witha similar cycle time, which for all cases was around 17 hours, so thatthe results within the runs were comparable.

The detailed reaction conditions as well as raw materials and finalanalytical results are shown Table 4, wherein “bad” indicates lower saltquality (higher APHA color) and “good” indicates better salt quality(lower APHA color). In Examples 1 and 4, as a result of running at ahigher hot oil temperature (wall temperature), the reaction temperatureitself increased to a higher value of about 187° C., and the oDCB usagewas also much larger, about 4 L/hr instead of less than 1 L/hr, comparedto the low temperature cases, namely Examples 2 and 3. Accordingly, theeffect on YI and Mz/Mw is a combined effect of reactor wall temperature,agitation speed, and lab reactor conditions that lead to higher reactiontemperature and higher oDCB usage.

TABLE 4 Ex 1 Ex 2 Ex 3 Ex 4 Bad BPANa₂ + Bad BPANa₂ + Good BPANa₂ + GoodBPANa₂ + Condition/property Harsh Condition Mild Condition MildCondition Harsh Condition ClPAMI charge (g) 355.00 326.12 326.06 322.32ClPAMI stoic (%) 0.15 0.15 0.15 0.15 BPANa₂ color (APHA 100%) 219 219 6363 # of stoic corrections 3 2 2 2 Polymerization time (hr) 17 17 17 17Hot oil temperature (° C.) 220 190-195 190-195 220 Reaction temperature(° C.) ~187 ~182 ~182 ~187 Agitation (rpm) 300 1000 1000 300 Quenchingtemperature (° C.) 170 170 170 170 Final % solids ~25 ~25 ~25 ~25Estimated boiled oDCB (L/hr) ~4 <1 <1 ~4 Solids (%) 6.9 6.9 7.0 6.2 HEG(ppm) 0 0 0 0 PEG (ppm) 16 13 16 19 Final Mw (kDa) 39.8 40.0 40.8 44.9Mz/Mw 1.683 1.626 1.610 1.668 Average YI of PEI 103 88 82 97 St. dev. YIof PEI 10 10 3 7

The effects of variables X1 (reaction conditions) and X2 (BPA Saltquality) are also illustrated in FIGS. 2 and 3.

-   -   BPA Salt quality effect: +6 YI units/+0.02 Mz/Mw    -   Reaction conditions effect: +15 YI units/+0.06 Mz/Mw

Examples 5-6

These examples show that phosphoric acid quenching temperature has animpact in YI of the polyetherimide polymer.

Unquenched polymer solution was taken from a master batch preparedaccording to the general procedure described above. The quenchingprocedure was followed to achieve pH below 3 using two temperatures,150° C. and 170° C. The color of the produced PEI was analyzed and theresults are shown in Table 5 as well as FIGS. 2-4. The data indicatethat there was an improvement of YI by decreasing the quenchingtemperature from 170° C. to 150° C.

TABLE 5 Quenching Example No. temperature (° C.) YI L a* b* Example 5(1^(st) Run) 170 114 79.4 9 78 Example 5 (2^(nd) Run) 170 114 79.8 9.678.7 Average 170 114 79.6 9.3 78.4 Example 6 (1^(st) Run) 150 104 82.54.7 71.7 Example 6 (2^(nd) Run) 150 101 83.2 4.1 69.6 Average 150 10380.9 7.3 75.3

These results show that it is possible, using one or all of an oiltemperature of 150° C. to 320° C., the disclosed mixing parameters, andthe low temperature quenching, to achieve a polyetherimide compositionhaving a YI of less than 93 to 50, or less than 90 to 50, or less than80 to 50, or less than 70 to 50. The YI is a predicted plaque value thatcan be determined by dissolving 0.5 grams of polyetherimide in 10 mL ofmethylene chloride, and measuring the YI of the resulting solution inaccordance with ASTM E313; and then converting the value to a predictedplaque YI value using Equation 2 above.

This disclosure is further illustrated by the following Embodiments,which are not intended to limit the claims.

Embodiment 1

A method for the manufacture of a polyetherimide composition, the methodcomprising: contacting a bis(phthalimide) having the formula

with an alkali metal salt of a dihydroxy aromatic compound having theformulaMO—Z—OMin an oil-jacketed reactor, in the presence of a catalyst and 0 to 15%,or 0 to 10% of a capping agent, and at an oil temperature of 150° C. to320° C., to form a polyetherimide comprising structural units having theformula

wherein in the foregoing formulae X is fluoro, chloro, bromo, iodo,nitro, or a combination thereof; R is an aromatic hydrocarbon grouphaving 6 to 27 carbon atoms, a halogenated derivative thereof, astraight or branched chain alkylene group having 2 to 10 carbon atoms, ahalogenated derivative thereof, a cycloalkylene group having 3 to 20carbon atoms, a halogenated derivative thereof, —(C₆H₁₀)_(z)— wherein zis an integer from 1 to 4, an aromatic hydrocarbyl moiety having from 1to 6 aromatic groups, and a divalent group of the formula

wherein Q¹ is —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— wherein y isan integer from 1 to 5, or a combination thereof; M is an alkali metal;Z is an aromatic C₆₋₂₄ monocyclic or polycyclic moiety optionallysubstituted with 1 to 6 C₁₋₈ alkyl groups, 1 to 8 halogen atoms, or acombination thereof; and n is an integer greater than 1; and wherein thepolyetherimide has a Yellowness Index of from less than 93 to 50.

Embodiment 2

The method of Embodiment 1, wherein the oil temperature is from 180° C.to 240° C.

Embodiment 3

The method of Embodiment 1, wherein the oil temperature is from 188° C.to 192° C.

Embodiment 4

The method of Embodiment 1, wherein the polyetherimide has a YellownessIndex of less than 90.

Embodiment 5

The method of Embodiment 1, wherein the polyetherimide has a YellownessIndex of less than 80.

Embodiment 6

The method of Embodiment 1, wherein the polyetherimide has a YellownessIndex of less than 70.

Embodiment 7

The method of Embodiment 1, wherein the reactor is mixed using anagitator with two sets of pitched turbine blades, with a blade to vesseldiameter ratio range of about 0.45 to 0.65, at a speed in a range fromabout 40 to about 90 revolutions per minute, in a reactor with a volumerange from about 20 to 35 cubic meters, and a cylindrical height todiameter ratio range of about 1.3 to about 1.6.

Embodiment 8

The method of Embodiment 7, wherein the agitator has two sets of 45°pitched turbine blades with a blade to vessel diameter ratio of about0.54 at a speed in a range from about 70 to about 86 revolutions perminute in a reactor with volume of about 28 cubic meters with acylindrical height to diameter ratio of about 1.45.

Embodiment 9

The method of Embodiment 1, further comprising quenching thepolymerization with an acid at a temperature of from 130° C. to 200° C.

Embodiment 10

The method of Embodiment 1, further comprising quenching thepolymerization with an acid at a temperature of from 145° C. to 155° C.

Embodiment 11

The method of Embodiment 9, wherein the acid is phosphoric acid.

Embodiment 12

A method for the manufacture of a polyetherimide composition, the methodcomprising: contacting a bis(phthalimide) having the formula

with an alkali metal salt of a dihydroxy aromatic compound having theformulaMO—Z—OM,in an oil-jacketed reactor, in the presence of a catalyst and 0 to 10%of a capping agent, and at an oil temperature of 150° C. to 320° C.,quenching the polymerization with an acid at a temperature of from 130°C. to 200° C., mixing the reactor using an agitator with two sets ofpitched turbine blades, with a blade to vessel diameter ratio range ofabout 0.45 to 0.65, at a speed in a range from about 40 to about 90revolutions per minute, in a reactor with a volume range from about 20to 35 cubic meters, and a cylindrical height to diameter ratio range ofabout 1.3 to about 1.6, and quenching the polymerization with an acid ata temperature of from 130° C. to 200° C., to form a polyetherimidecomprising structural units having the formula

wherein in the foregoing formulae X is fluoro, chloro, bromo, iodo,nitro, or a combination thereof; R is an aromatic hydrocarbon grouphaving 6 to 27 carbon atoms, a halogenated derivative thereof, astraight or branched chain alkylene group having 2 to 10 carbon atoms, ahalogenated derivative thereof, a cycloalkylene group having 3 to 20carbon atoms, a halogenated derivative thereof, —(C₆H₁₀)_(z)— wherein zis an integer from 1 to 4, an aromatic hydrocarbyl moiety having from 1to 6 aromatic groups, and a divalent group of the formula

wherein Q¹ is —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— wherein y isan integer from 1 to 5, or a combination thereof; M is an alkali metal;Z is an aromatic C₆₋₂₄ monocyclic or polycyclic moiety optionallysubstituted with 1 to 6 C₁₋₈ alkyl groups, 1 to 8 halogen atoms, or acombination thereof; and n is an integer greater than 1; and wherein thepolyetherimide has a Yellowness Index of from from less than 93 to 50.

Embodiment 13

The method of Embodiment 12, wherein the polyetherimide has a YellownessIndex of less than 80.

Embodiment 14

The method of Embodiment 12, wherein the polyetherimide has a YellownessIndex of less than 70.

Embodiment 15

The method of Embodiment 12, wherein the agitator has two sets of 45°pitched turbine blades with a blade to vessel diameter ratio of about0.54 at a speed in a range from about 70 to about 86 revolutions perminute in a reactor with volume of about 28 cubic meters with acylindrical height to diameter ratio of about 1.45.

In any of the foregoing embodiments,

All molecular weights in this application refer to weight averagemolecular weights unless indicated otherwise. All such mentionedmolecular weights are expressed in Daltons. All ASTM tests are based onthe 2003 edition of the Annual Book of ASTM Standards unless otherwiseindicated.

The terms “a” and “an” do not denote a limitation of quantity, butrather denote the presence of at least one of the referenced item. “Or”means “and/or.” As used herein, “combination thereof” is inclusive ofone or more of the recited elements, optionally together with a likeelement not recited. It is to be understood that any one or more of thedescribed element(s) of the embodiments can be combined in any suitablemanner in the various embodiments.

Various numerical ranges are disclosed in this patent application.Because these ranges are continuous, they include every value betweenthe minimum and maximum values. Unless expressly indicated otherwise,the various numerical ranges specified in this application areapproximations. The endpoints of all ranges directed to the samecomponent or property are inclusive of the endpoint and independentlycombinable.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“−”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group. The term “alkyl” includes C₁₋₃₀branched and straight chain, unsaturated aliphatic hydrocarbon groupshaving the specified number of carbon atoms. Examples of alkyl include,but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl,s-butyl, t-butyl, n-pentyl, s-pentyl, n- and s-hexyl, n- and s-heptyl,and, n- and s-octyl. The term “aryl” means an aromatic moiety containingthe specified number of carbon atoms, such as to phenyl, tropone,indanyl, or naphthyl.

“Substituted” means that the compound or group is substituted with atleast one (e.g., 1, 2, 3, or 4) substituents instead of hydrogen, whereeach substituent is independently nitro (—NO₂), cyano (—CN), hydroxy(—OH), halogen, thiol (—SH), thiocyano (—SCN), C₁₋₆ alkyl, C₂₋₆ alkenyl,C₂₋₆ alkynyl, C₁₋₆ haloalkyl, C₁₋₉ alkoxy, C₁₋₆ haloalkoxy, C₃₋₁₂cycloalkyl, C₅₋₁₈ cycloalkenyl, C₆₋₁₂ aryl, C₇₋₁₃ arylalkylene (e.g,benzyl), C₇₋₁₂ alkylarylene (e.g, toluyl), C₄₋₁₂ heterocycloalkyl, C₃₋₁₂heteroaryl, C₁₋₆ alkyl sulfonyl (—S(═O)₂-alkyl), C₆₋₁₂ arylsulfonyl(—S(═O)₂-aryl), or tosyl (CH₃C₆H₄SO₂—), provided that the substitutedatom's normal valence is not exceeded, and that the substitution doesnot significantly adversely affect the manufacture, stability, ordesired property of the compound. When a compound is substituted, theindicated number of carbon atoms is the total number of carbon atoms inthe group, including those of the substituent(s).

All references cited herein are incorporated by reference in theirentirety. While typical embodiments have been set forth for the purposeof illustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations, and alternatives can occur to one skilled in the artwithout departing from the spirit and scope herein.

What is claimed is:
 1. A method for the manufacture of a polyetherimidecomposition, the method comprising: contacting a bis(phthalimide) havingthe formula

with an alkali metal salt of a dihydroxy aromatic compound having theformulaMO—Z—OM, in an oil-jacketed reactor, in the presence of a catalyst and 0to 10% of a capping agent, and at an oil temperature of 150° C. to 320°C., or 180° C. to 240° C., or 188° C. to 192° C., to form apolyetherimide comprising structural units having the formula

wherein in the foregoing formulae X is fluoro, chloro, bromo, iodo,nitro, or a combination comprising at least one of the foregoing; R isan aromatic hydrocarbon group having 6 to 27 carbon atoms, a halogenatedderivative thereof, a straight or branched chain alkylene group having 2to 10 carbon atoms, a halogenated derivative thereof, a cycloalkylenegroup having 3 to 20 carbon atoms, a halogenated derivative thereof,—(C₆H₁₀)_(z)— wherein z is an integer from 1 to 4, an aromatichydrocarbyl moiety having from 1 to 6 aromatic groups, and a divalentgroup of the formula

wherein Q¹ is —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— wherein y isan integer from 1 to 5, or a combination thereof; M is an alkali metal;Z is an aromatic C₆₋₂₄ monocyclic or polycyclic moiety optionallysubstituted with 1 to 6 C₁₋₈ alkyl groups, 1 to 8 halogen atoms, or acombination thereof; and n is an integer greater than 1; and wherein thepolyetherimide has a Yellowness Index of from less than 93 to
 50. 2. Themethod of claim 1, wherein the reactor is mixed using an agitator withtwo sets of pitched turbine blades, with a blade to vessel diameterratio range of about 0.45 to 0.65, at a speed in a range from about 40to about 90 revolutions per minute, in a reactor with a volume rangefrom about 20 to 35 cubic meters, and a cylindrical height to diameterratio range of about 1.3 to about 1.6.
 3. The method of claim 2, whereinthe agitator has two sets of 45° pitched turbine blades with a blade tovessel diameter ratio of about 0.54 at a speed in a range from about 70to about 86 revolutions per minute in a reactor with volume of about 28cubic meters with a cylindrical height to diameter ratio of about 1.45.4. The method of claim 1, further comprising quenching thepolymerization with an acid at a temperature of from 130° C. to 200° C.,or from 145° C. to 155° C.
 5. The method of claim 4, wherein the acid isphosphoric acid.
 6. The method of claim 1, wherein X is chloro; each Ris independently a divalent group of formulas

wherein Q′ is —O—, —S—, —C(O)—, —SO₂—, —SO—, —C_(y)H_(2y)— wherein y isan integer from 1 to 5 or a halogenated derivative thereof (whichincludes perfluoroalkylene groups), or —(C₆H₁₀)_(z)— wherein z is aninteger from 1 to 4; Z is a group of the formula

wherein R^(a) and R^(b) are each independently the same or different,and are a halogen atom or a monovalent C₁₋₆ alkyl group; p and q areeach independently integers of 0 to 4; c is 0 to 4; X^(a) is a singlebond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—, or a C₁₋₁₈ organic bridginggroup; and n is 5 to
 500. 7. The method of claim 6, wherein R ism-phenylene, p-phenylene, bis(4,4′-phenylene)sulfone,bis(3,4′-phenylene)sulfone, bis(3,3′-phenylene)sulfone, or a combinationcomprising at least one of the foregoing; and Z is a divalent group ofthe formula

wherein Q is —O—, —S—, —C(O)—, —SO₂—, —SO—, or —C_(y)H_(2y)— wherein yis an integer from 1 to 5 or a halogenated derivative thereof.
 8. Themethod of claim 7, wherein Q is 2,2-isopropylidene.
 9. The method ofclaim 1, further comprising up to 15 mole % of a capping agent.
 10. Themethod of claim 9, wherein the capping agent is of the formulaM²-O—Z² wherein M² is an alkali metal and Z² is derived from amonohydroxy aromatic compound of the formula

wherein R^(c) and R^(d) are each independently a halogen atom or amonovalent C₁₋₆ alkyl group; r and s are each independently integers of0 to 4; c is zero to 4; t is 0 or 1, provided that when t is zero, X^(b)is hydrogen or a C₁₋₁₈ alkyl group, and when t is 1, X^(b) is a singlebond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—, or a C₁₋₁₈ organic bridginggroup.
 11. The method of claim 10, wherein Z² is of the formula

or a combination comprising at least one of the foregoing.
 12. Themethod of claim 1, wherein the contacting the bis(phthalimide) is at anoil temperature of 150° C. to 320° C., in the presence of a catalyst andup to 15 mole % of a capping agent, based on the total moles of thealkali salt the dihydroxy aromatic compound and the capping agent; thereactor contents are mixed using an agitator with two sets of pitchedturbine blades, with a blade to vessel diameter ratio range of about0.45 to 0.65, at a speed in a range from about 40 to about 90revolutions per minute, in a reactor with a volume range from about 20to 35 cubic meters, and a cylindrical height to diameter ratio range ofabout 1.3 to about 1.6; the method further comprises quenching thepolymerization with an acid at a temperature of from 130° C. to 200° C.;and the polyetherimide has a Yellowness Index of from less than 93 to50r.
 13. The method of claim 12, wherein the agitator has two sets of45° pitched turbine blades with a blade to vessel diameter ratio ofabout 0.54 at a speed in a range from about 70 to about 86 revolutionsper minute in a reactor with volume of about 28 cubic meters with acylindrical height to diameter ratio of about 1.45.
 14. The method ofclaim 12, wherein the polyetherimide has a Yellowness Index of from lessthan 70 to
 50. 15. The method of claim 12, wherein the polyetherimidehas a Yellowness Index of from less than 80 to
 50. 16. The method ofclaim 12, wherein R is m-phenylene, p-phenylene,bis(4,4′-phenylene)sulfone, bis(3,4′-phenylene)sulfone,bis(3,3′-phenylene)sulfone, or a combination comprising at least one ofthe foregoing; and Z is a divalent group of the formula

wherein Q is —O—, —S—, —C(O)—, —SO₂—, —SO—, or —C_(y)H_(2y)— wherein yis an integer from 1 to 5 or a halogenated derivative thereof.
 17. Themethod of claim 16, wherein Q is 2,2-isopropylidene.
 18. The method ofclaim 1, wherein the polyetherimide has a Yellowness Index of from lessthan 80 to
 50. 19. The method of claim 1, wherein the polyetherimide hasa Yellowness Index of from less than 70 to 50.